Product and synthesis thereof



Patented July 13, 1943 PRODUCT AND SYNTHESIS THEREOF John Carl Sauer,Wilmington, Del., assignor to E. I. du Pont de Nemours &' Company,Wilmington, 'Del., a corporation of Delaware No Drawing. ApplicationJuly 25, 1940, Serial No. 347,555

Claims. (01. 260-561) This invention relates to new compositions ofmatter and more particularly .to amides and their preparation. 2 I

This application is a continuation-in-part of my copending applicationsSerial Nos. 234,843 and 234,844, filed October 13, 1938.]

Amides are of useas intermediates in a num-.

ber of chemical syntheses, and certain long chain vision of a newprocess for this purpose. Other objects will appear hereinafter.

These objects are accomplished by the following invention wherein analpha acyl ethenone having at least thirteen carbon atoms is reactedwith a basic compound having at least one hydrogen on ammonia typenitrogen. "--In the preferred practice of thisinventionbetaketocarbonamides are prepared by adding anhydrous ammoniaor anhydrous amines, bearing at least one amino hydrogen atom, to asolution, in

an inert solvent, of an alpha acyl ethenone. The alpha acyl ethenone maybe prepared, as disclosed in my copending applications Serial Nos.234,843 and 234,844 (now U. S. Pa+ent 2,238,826) by the reaction of atertiary amine, e. g., triethylamine, and at least one-primary acidhalide,

i. e., one containing the acid halide group -CO-X attached to a carbonbearing at least two hydrogen atoms, in an inert anhydrous solvent atroom temperature. Removal of the tertiary amine'hydrochloride byindirect .filtering after the reactants have stood from 12 to 24 hoursgives a solution of the acyl ethenone. The

acyl ethenones must be prepared under anhydrous conditions andmaintained in an anhyrous environment until used. The acyl ethenonessuitable for the purpose of this invention have at least thirteen carbonatoms and have the formula n-cm-co-o=o0 it being a monovalent organicradical which,

from the method of preparation, is chemically inert at temperatures upto 170 C. to tertiary amines, acid halides and ethenones. R ispreferably a hydrocarbon radical such as aryl, aral- 'ill hydrogen onammonia ration of the amides. can be concentrated by kyl, cycloalkyl andopen chain 'alkyl but may contain inert groups such as carbalkox'y,alkoxy, aryloxy, aralkoxy, keto, tertiary amide, halogen attached toaromatic carbon or aliphatic heterocyclic groups. R may be hydrogenbut,.in view of the method of preparation of the acyl ethenones, ispreferably a monovalent organic radicalwith the chemical inertness of Rand preferably hydrocarbon. R may be the same as R or may be different.vAn especially preferred class of ethenones is that wherein R and Rchain alkyl. R and R must total at least nine and for one of the mostimportant fields of usefulness, the waterproofing field, preferablytotal at least twenty.

Amides are prepared from these acyl ethenones, in the preferred practiceof the invention, by adding ,the...basic compound containing typenitrogen to the acyl ethenone of at least thirteen carbon atoms in aninerttsolvent therefor. Reaction generally proceeds rapidly with thegeneration of some heat, and generally the-amide precipitates from thesolution from which it is filtered and is purified by recrystallizationfrom a suitable solvent. In some cases the resulting amide is soluble inthe solvent in'which it is prepared. In these instances the solvent isremoved at low temperature under diminished pressure and the resultingamide is recrystallized from a suitable solvent. Since the acylethenones are usually prepared in solutions of 5 to 10 per centconcentration, these solutions are generally used as such in the prepa-The solutions, however, removing the solvent at low temperatures underreduced pressure, or all the solvent can be removed in this mannerbefore reacting the acyl ethenone with ammonia or a suitable amine.This, however, is not as satisfactory as when a solvent is used.

A particularly useful class of products coming within the broad scope ofthis, invention, namely that of amides containing at leastone hydrogenatom on the amide nitrogen may be prepared by the reaction of acylethenones on basic compounds having two hydrogens on the same ammoniatype nitrogen and are useful intermediates for the synthesis of waterrepellent materials and related products. Synthesis of water repellentmaterials, as outlined in Example I below, is effected by condensing thebeta-ketocarbonamide with paraformaldehyde and an anhydrous hydrohalcgenacid in an inert solvent, and subsequently reacting the isolatedamidomethyl halide with a tertiary amine.

are open I The more detailed practice of the invention is illustrated bythe following examples, wherein parts given are by weight. There are ofcourse many forms of the invention. other than these specificembodiments.

- Example I A mixture of eicosanoic and docosanoic acids, I

- is allowed to stand for 20 hours at room temperature and thenfiltered. A total of 21 parts of triethylamine hydrochloride isseparated by this filtration. The reaction forsimplicity is repre-Sented as follows:

The product is a mixture of acyl ethenones wherein the two R's are thesame or different, the R's having 18 and 20 carbon atoms.

To a solution of 45 parts of the acyl ethenone mixture in anhydrousbenzene (7,040 parts) is added hexamethylenediamine (54 parts). themixture has stood for several hours to insure complete reaction, anadditional 100 parts of hexamethylenediamine is added. The reactorvessel is then set aside at room temperature overnight duringwhich timethe reaction product crystallizes from the solution. A yield of 45% ofAfter the theory of purified product is obtained. The

product is represented by the formula RomeooncoNmomnNncocnoocma in whichR and R contain 18 or 20 carbon atoms and are alike or different. Themelting point of the product is 88-93 C.

To the amide (205 parts) in dry benzene (1100 parts) is addedparai'ormaldehyde (18 parts). The mixture is stirred at 50 to 60 C. for2.5 hours while a stream of dry hydrogen chloride is bubbled through thereaction mixture. After separation of the water layer, the benzene isremoved under reduced pressureat 40 C. until onlythe chloromethylderivative is left. Dry pyridine in excess is added until an homogeneoussolution results upon being stirred. Most of the excess pyridine isremoved under reduced pressure and the last traces removed in a vacuumdesiccating compartment.

A portion of the product which comprises chiefly theamidomethylpyridinium chloride salt, is analyzed for active ingredientconte t by the following method. To a weighed sam e of the product isadded ice and methanol and the cold N calculated for C42Ha302N. Theproduct The water repelling agent (5 parts) is-pasted with ethanol (6parts) at 40-43 C. Water parts) at 40-43 C. is added with stirring, and

Repellency Initial Laundered A cloth having a repellency of will, wheninclined at a 45 angle, completely repel 250 cc. of water at 80 F.sprayed from a height of 6 inches directly above, and none will cling tothe cloth. A repellency of 90 means that a few drops of water cling tothe cloth but can be completelyremoved by shaking. A repellency of 50means that the upper surface of the cloth is wetted under theexperimental conditions, but the water does not penetrate the cloth.

The laundering treatment consists in boiling the" sample in a 0.1% soapsolution for onehour, rinsing thoroughly and drying.

Example II The acid chlorides ofthe mixture of eicosanoic and docosanoicacids are converted to the acyl ethenones as illustrated in Example I.The acyl ethenones are converted to the corresponding amides by bubblinganhydrous ammonia through the benzene solution of the ethenones. (Carbontetrachloride solutions may also be-used.) The benzene solution ischilled, filtered, and the precipitate recrystallized from aqueousethanol. The melting point is 949'I C. Analysis of-the product showed2.5% N as compared with 2.3% has the general formula RCHQCOCHCONH;

in which R and R contain 18 or 20 carbon atoms and are alike ordifferent.

To these amides parts) in dry benzene (970 parts) is addedparaformaldehyde (22 parts) and a stream of dry hydrogen'chloride isbubbled into the reaction mixture with constant stirring for a period of2.5 hours. The reaction mixture is maintained at a temperature of 55-60C.

' The water layer is separated and the benzene solution is titrated withalkali immediately. This analysis determines what portion of thechlorine is present as pyridine hydrochloride. A-second weighed sampledissolved in methanol is heated at reflux temperature from 3 to 24 hoursand then titrated with alkali. The heating step converts all thequaternary ammonium salt to pyridine hydrochloride and the titrationwith standremoved under'reduced pressure. After removal of the solvent,the material is melted on the steam bath and pyridine (43 parts) isadded with rapid stirring and cooling. After the excess pyridine.

has been removed under reduced pressure a sample is analyzed forchlorine and found to contain 6.6% whereas the value calculated for Theamidomethylpyridinium Sen- (6 parts) obtained as described above, ispasted with ethanol parts) at 40 to 43- C. Water (90 parts) at 40-43 C.is added with stirring. Sodium acetate (2 parts) in water (4 parts) at40-43 C. is added to give a pH of approximately 5. This solutioncontains 2.4% of active ingredient."

. 5 The following experiment is run in duplicate:

A piece of cotton jean cloth is dipped into the solution and allowed tobecome saturated, mg in a mechanical wiinger and the process repeated;The weight of the wet cloth is twice its dry weight. It is dried andbaked for 5 minutes at 150 C. The results of spray tests. made on thetwo samples are as follows:

Repellency Initial Laundered Example In drous ammonia is bubbled intothe solution of the acyl ethenone having the formula IOfiIICHICOC=C=O A,quantitativ yield of the alpha-dodecanoyl dodecanamid is obtained. Afterthree recrystallizations from ethanol, the product melts at 110 to 111C;

Example VI Dodecanoyl chloride is converted to the acyl ethenone in thesame manner as outlined in Example V. To an ether solution of the acylethenone is added aniline and the reaction mixture allowed to standovernight. The following "morning the precipitate which formed isiiltered reduced pressur and theproduct carefully dried.

The product analyzed for 2.68% nitrogen compared with 2.56% calculatedfor CaaHcaOzN.

The product can be converted-to the amidomethylpyridinium halide by themethod illustrated in Example 11.

The amide has the formula oi nucnlcocnconn,

Hi1 Example IV Linseed oil acid chlorides (B. P. 180-3 c./s mm), amixture of the C13 multiply. unsaturated straight chain acid chlorides,are converted to the acyl ethenones by adding, during a 5 minute period,triethylamine (25.5 parts) to a solution of the linseed oil acidchlorides (75 partshin Precipitation of anhydrous ether (720 parts)thiethylamine hydrochloride begins immediately, the reaction mixture isplaced under an atmos-' phere of nitrogen and, after 2 hours at roomtemperature, .the reaction vessel is maintained at -40 F. for threedays. The thiethylamine hydrochloride is separated by filtering, and thefiltrate concentrated to 200'parts under reduced pressure.

Gaseous anhydrous ammonia is bubbled into a concentrated solution of theacyl ethenone in anhydrous ether. The precipitated amide is washed withether, dried, and analyzed for 2.8% nitrogen whereas the valuecalculated for CsoHaaOzN is 2.6%; g

The product can be converted to the amidoand recrystallized twice fromethanol. The alpha-dodecanoyldodecanilide has a melting point 01' 84 to85 C. and analyzes for 78.46% carbon, 11.77% hydrogen and 3.18%nitrogenwhich compares with the values calculated for CaoHnOaN of 78.72%carbon, 11.24% hydrogen and 3.06% nitrogen.

' .Emmple VII Octadecanoyl chloride is 'conv'erted-to-the acyl ethenoneby adding triethylamine (101 parts) to a solution of octadecanoylchloride (76 parts)' in anhydrous benzene (880 parts), allowing thereaction mixture to stand for 24 hours at room temperature and separatinthe triethylam'ine hydrochloride formed by filtering. -To the filtrateis added 1,5-aminonaphthol (40 parts). The reaction-mixture is allowedto stand at room temperature for hours, and is then heated for 1 hour at40-50 C. The reaction mixture is washed with water containing a smallamount of sodium has'the formula. 40

.sulfite dissolved in it. The product is recrystallize'd fromether-petroleum ether mixture. It

CilHs: OreHsaCHaCOZiHCONH 7 Example VIIIAlpha-octadecanoyloctadecanamide is prepared by adding triethylamine(233 parts) to a solution of 'octadecanoyi chloride (694 parts) incarbon tetrachloride (5760 parts), allowing the reaction mixture tostand for 16 hours, separating the aminehydrochloride by filtering, andbubbling into the filtrate an excess of anhydrous ammoniav at roomtemperature whereupon the alphaoctadecanoyloctadecanamide crystallizesfrom solution. After recrystallization from ethanol-acetone mixture, theproduct, melting at 104 C., is obtained in a 95 per cent yield andcontains 2.22 nitrogen, the value calculated for CseH'uOaN being 2.55%,

methylpyridinium halide by the method illustrated in Example 11.

Ei'cample V To triethylamine (52 parts) in anhydrou diethyl ether (1050parts) is added dodecanoyl 'chloride (109 parts) and the reactionmixture is allowed to stand 24 hours before the amine hydrochloride isremoved by filter 'zgt. Gaseous anhy- The products of the presentinvention have the generic formula ia-co-cHR -cd-Nmnw wherein R and Bhave the values given above, are preferably both hydrocarbon and total.at least nine and preferably twenty carbon atoms, R is hydrogen or amonovalent organic radical, and R is the non-amino residue of the basiccompound having hydrogen on ammonia type nitro- -'gen. :2:represents-the number of carbonamido residues in the compound and alsothe number cycloaliphatic, araliphatic or aromatic and is preferablyhydrocarbon. R may be all of these and may bemonovalent or polyvalent(as in the diamlnes) RF and R may be unsubstituted, or

substituted as illustrated in Example VII.- These substituted radicalsmay contain dye coupllng nuclei as is further illustrated in ExampleVII. In addition to the aromatic dye coupling nuclei, both R. and R canbe long chain radicals useful in the preparation of intermediates forcolor photography. I

The acyl ethanone intermediates for the preparation of thebeta-ketocarbonamides may be prepared, as disclosed in my copendingapplications above identified, in anhydrous inert solvents byreactionvof the corresponding acid chlorides with tertiary amines.Removal of the tertiary amine hydrochloride gives a solution of the acylethenone which can be reacted readily with an amine or with ammonia.Solvents 'suitable'for acyl ethenone preparation are also admirablysuited for the subsequent amidation reaction. Any solvent whichdissolves but is inert toward acyl halides, tertiary amines or acylethenones is operable. including ethers, aromatic or aliphatichydrocarbons, aromatic and aliphatic chlorinated hydrocarbons can beemployed, including anhydrous benzene, petroleum ether, petroleumnaphtha, di-

ethyl ether, di-isopropyl ether, carbon tetrachlo ride,trichloroethylene, toluene, and other related solvents that will-notreact with ammonia or amines under the conditions required for amide-'-tion. Chlorinated hydrocarbons not suitable as beta-chloroethers. v Theonly acyl halides which can be converted to acyl ethenones andsubsequently to amides falling within the scope of this invention areThe inert radicals attached to the CH2COX amines produces the mostdesirable products, for

' when the resulting amide nitrogen is hydrogen crystallized from asuitable solvent.

bearing, subsequent reaction with paraformaldehyde, an anhydroushydrohaiogen acid, and a tertiary amine produces products that areuseful as water repellents and as textile. treating agents. Amidation iseifected by adding any of the amines described above in an anhydrousform to a solution of the acyl ethenone. The presence of a solvent isnot necessary, however, for the amidation reaction. The solvent may beremoved under reduced pressure at a low temperature and the remainingacyl ethenone'reacted directly with the amine in the absence of asolvent. If the amine is low boiling and the excess can be removed atlow temperature under reduced pressure, the resulting amide can be usedin any subsequent reaction without furtherpurification or can be re-Amides prepared in solvents frequently precipitate from these solventsand may be used in subsequent reaction without further purification, orcan be re- Therefore a wide variety'of solvents solvents include benzylchloride and alphaor group are so chosen that they total at least nineand preferably twenty carbons. Examples of such halides are hendecanoylchloride, dodecanoyl chloride, tridecanoyl chloride, tetradecanoylohlocrystallized from suitable solvents. Some of the amides, however,have been found to be soluble in the solvents in which they wereprepared. In these cases the solvent is removed at low temperaturesunder reduced pressure, and again the amide can be used as isolated orcan be purified by recrystallization from a suitable solvent. Aminessuitable for amidating the acyl ethenones include methylamine,ethylamine, ethanolamine, propylamine, butylamine, isobutylamine,cyclohexylamine, pentylamine, cyolopentylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, hendecylamine, dodecylamine,tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, nonadecylamine, eicosylamine,heneicosylamine, docosylamine, hentriacontylamine, hexacontylamine,aniline, p-hydroxyaniline, naphthylamine, aminophenanthrene,aminoanthracene, aminochrysene, dimethylamine, diethyiamine,dibutylamine, N-methylhexylamine, N-methylcyclohexylamine, piperldine,,morpholine, N- methylaniline, p-methoxy-N-methylaniline, pyrrole,pyrroline, pyrrolidine, 1,2,3-dioxazole, 1,3,2- dioxazole,1,2,4-dioxazole, 1,3,4-dioxazole, indole, isoinclole, 1,2-benzisoxazine,dipropylamine, di-

' pentylamine, di-isobutylamine, N-methyloctaride, i-phenoxybutanoylchloride, cyclohexyL :1

acetyl chloride, furyldecanoyl chloride, S-phenylpropanoyi chloride,octadecen-Q-oyl chloride, nonadecanoyl chloride, eicosanoyl chloride,docos} anoyl chloride and hexacosanoyl chloride. Mixetures of acidchlorides can be used but the lower molecular weight acid chlorideshould contain at least 3 carbon atoms. Any acyl ethenone of the formulaR-CH2--COCR=CO wherein R and R are as above may be used.

In the preparation of the amides, any basic compound having hydrogen onammonia type nitrogen may be employed including ammonia,

hydrazine, hydroxylamine, and amines having at least one hydrogen on theamino nitrogen. While amines, etc. having other groups reactive with theacyl ethenones may be employed, it is preferred that the basicammonia/type compound have only the =NH grouping reactive with acylethenones.

' Amidation with ammonia and with primary decylamine,N-methylheptadecylamine, N-ethyleicosylamine, N-methylheneicosylamine,N- methyldocosylamine, V N-methylhexacosylamine, dioctadecylamine,didodecylamine, and dipentylamine, ethylenediamine, trimethylenediamine,tetramethylenediamine, pentamethylenediamine,

hexamethylenediamine, beta-methylhexamethylenediamine,beta-phenylhexamethylenediamine,

decamethylenediamine, tridecamethylenediamine,

- bigesimethylenediamine,

clobigesimethylenedi amine, m-diaminobenzene, 1,5-diaminonaphthalene,3,6-dioxa-1,8-diamino-octane, heptamethylenediamine,nonamethylenediamine, octamethylenediamine, hendecamethylenediamine,dodecamethylenediamine, tetradecamethyienediamine,pentadecamethylenediamine, hexadeca methylenediamine,heptadecamethylenediamine, octadecamethylenediamine,nonadecamethylenediamine, N,N-dimethylhexamethylenediamine, N,N'didodecamethyienedobigesimethyienedlamine, piperazine,N,N-dimethyl-1,3-diamino benzene, N,N'-diethyiethylenediamine,N,N'-dimethylpropylenediamine, N,N-dimethylbutylene= diamine,N,N'-dimethyipentamethylenediamine, N,N'-dimethylheptamethylenediamine,methyloctamethylenediamine,

nonamethylenediamine, N,N' dimethyldeca- 3. Process which comprisesreacting an acyl metlrvlenediarnine. N,N dimethyloctadecaethenone'of theformula methylenediamine, N-methyl-1,4-diaminobenzene,N-methylhexamethylenediamine, N-methylethylenediamine,4-aminopiperidine, N-methylpropylenediamine, N-ethylbutylenediamine, N-heptyltetradecamethylenediamine, N-propyldecamethylenediamine,N-methyloctadecamethylenediamlne, and N-methyloctamethylenediamine. 'lfhe term aliphatic hydrocarbon monamine having hydrogen on aminonitrogen is used to desigwherein .R and R are monovalent aliphatichydrocarbon radicals totalling at least nine carbon atoms with a basiccompound having a hydrogen bearing ammonia type nitrogen of the classconirate a monoamine which, apart from the amino nitrogen and hydrogenattached thereto, is allphatic hydrocarbon.

' The products of this invention are useful inter-,

mediates in the synthesis of water repellents, textile treating agents,and other products of commercial importance.

The above description and examples are intended to be illustrative only.Any modification of or variation therefrom which conforms to the spiritof the invention is intended to be included within the scope of theclaims.

What is claimed is: a

1. A beta-ketocarbonamide of the formula wherein R, R and R. aremonovalent aliphatic hydrocarbon radicals and R} and R total at leastnine carbon atoms.

2. A beta-ketocarbonamide of the formula where R and R are alkylradicals totalling at least nine carbon atoms.

sisting of ammonia and aliphatic hydrocarbon monoamines having hydrogenon amino nitrogen.

4. A beta-ketocarbonamide of the formula RCHzCOCHR -CO---NH2 where R andR are monovalent aliphatic hydrocarbon radicals totalling at leasttwenty carbon wherein R and R ,.are monovalent aliphatic hydrocarbonradicals. totalling at least nine carbon atoms and R is a member of theclass consisting of hydrogen and monovalent aliphatic hydrocarbonradicals.

10. Alpha-octadecanoyloctadecanamide.

JOHN CARL SAUER.

. CERTIFICATE OF CORRECTION a Patent ,5 5,938- c July 15, 1 15,

JOHN CARL SAUER.

It is hereby certified that error appears inthe printed specification ofthe above numbered patent requiring correction as follows: Page 5, firstcolumn, line 52, claim 2, for that portion of the formula reading NHRread --.-NH and that the said Letters Patent should be read with thiscorrection therein that the same may conform to the record of. the casein the Patent Office.

Signed and sealed this 7th day of September, A'. D. 1915.

- Henry Van Arsdale,

(Seal) Acting Commis'sionerof Patents.

